Sprayer

ABSTRACT

To provide a sprayer with high safety, specifically, a sprayer from which a component to be sprayed is incombustible and which imposes less environmental burden. A sprayer comprising a container, a propellant composition containing 1-chloro-2,3,3,3-tetrafluoropropene contained in the interior of the container, and a spray unit to spray the propellant composition to the outside of the container, wherein the propellant composition to be sprayed satisfies (1) in a predetermined combustion test, the propellant composition to be sprayed is evaluated to “have no combustibility”, and (2) the global warming potential (100 years) in accordance with Intergovernmental Panel on Climate Change (IPCC), Fifth assessment report, is less than 10, throughout the entire period over which the sprayer is used.

TECHNICAL FIELD

The present invention relates to a sprayer. Particularly, it relates toa sprayer having high safety and imposing less environmental burden.

BACKGROUND ART

Heretofore, in a one component sprayer which sprays a propellant itselfsuch as a dust blower and a two component sprayer which sprays achemical agent together with a propellant such as an aerosol product, asthe propellant, a hydrofluorocarbon (HFC), for example,1,1,1,2-tetrafluoroethane (HFC-134a) has been used. Among HFCs, HFC-134ais incombustible and has less influence over the ozone layer, but isknown to have a high global warming potential (GWP).

Accordingly, in recent years, a hydrofluooroolefin (HFO), ahydrochlorofluoroolefin (HCFO) and a chlorofluoroolefin (CFO) having acarbon-carbon double bond, which is easily decomposed by OH radicals inthe air, and thereby having less influence over the ozone layer and alow GWP, have been expected (for example, Patent Document 1). In thisspecification, unless otherwise specified, a saturated HFC will bereferred to as a HFC and is distinguished from a HFO. Further, a HFC maysometimes be referred to as a saturated hydrofluorocarbon.

However, 1,3,3,3-tetrafluoropropene (HFO-1234ze) and2,3,3,3-tetrafluoropropene (HFO-1234yf), which are HFOs which have beenwidely used in recent years, are known to have combustibility and theirsafety are of concern.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: JP-A-2016-104873

DISCLOSURE OF INVENTION Technical Problem

Under these circumstances, it is an object of the present invention toprovide a sprayer with high safety, specifically, from which a componentto be sprayed is incombustible and which imposes low environmentalburden.

Solution to Problem

The present invention provides a sprayer having the followingconstitutions.

[1] A sprayer comprising a container, a propellant compositioncontaining 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) containedin the interior of the container, and a spray unit to spray thepropellant composition to the outside of the container,

wherein the propellant composition to be sprayed satisfies the followingrequirements (1) and (2) throughout the entire period over which thesprayer is used:

(1) in the following combustion test, the propellant composition to besprayed is evaluated to “have no combustibility”:

in combustion test carried out with respect to a mixture of a specimenand air in a container controlled at 60° C.±3° C. under 101.3 kPa±0.7kPa in facilities as specified in ASTM E-681-09, when the mixture has nocombustibility in the entire range of a proportion of the specimen tothe total volume of the mixture being higher than 0 vol % and up to 100vol %, such a specimen is evaluated to “have no combustibility”; in thecombustion test, in a gaseous phase in the vicinity of the center of thecontainer, a fire is made by discharge ignition under 15 kV at 30 mA for0.4 second, spread of flame is visually confirmed, and when the angle ofspread of the flame upward is less than 90 degrees, such a specimen isevaluated to have no combustibility;

(2) the global warming potential (100 years) in accordance withIntergovernmental Panel on Climate Change (IPCC), Fifth assessmentreport, is less than 10.

[2] The sprayer according to [1], wherein HCFO-1224yd consists of(Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and(E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), and theproportion of HCFO-1224yd(Z) to the total amount of HCFO-1224yd is atleast 80 mass % and at most 100 mass %.[3] The sprayer according to [1] or [2], wherein the propellantcomposition further contains a hydrofluoroolefin.[4] The sprayer according to [3], wherein the hydrofluoroolefin containsat least one member selected from 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) and1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz).[5] The sprayer according to any one of [1] to [4], wherein thepropellant composition comprises HCFO-1224yd(Z) and(E)-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and the proportion ofHCFO-1224yd(Z) is at least 20 mass % and less than 100 mass % to thetotal mass of HCFO-1224yd(Z) and HFO-1234ze(E) in a gaseous phaseportion in the container filled with the propellant composition so thatthe liquid phase portion is 90 vol %.[6] The sprayer according to any one of [1] to [4], wherein thepropellant composition comprises HCFO-1224yd(Z) and HFO-1234yf, and theproportion of HCFO-1224yd(Z) is at least 30 mass % and less than 100mass % to the total mass of HCFO-1224yd(Z) and HFO-1234yf in a gaseousphase portion in the container filled with the propellant composition sothat the liquid phase portion is 90 vol %.

Advantageous Effects of Invention

According to the present invention, a sprayer with high safety,specifically, a sprayer from which a component to be sprayed isincombustible and which imposes low environmental burden, can beprovided.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a schematic view illustrating a use example of one example ofa one component type of the sprayer of the present invention.

FIG. 1B is a schematic view illustrating a use example of one example ofa one component type of the sprayer of the present invention.

FIG. 2A is a schematic view illustrating a use example of one example ofa two component type of the sprayer of the present invention.

FIG. 2B is a schematic view illustrating a use example of one example ofa two component type of the sprayer of the present invention.

DESCRIPTION OF EMBODIMENTS

Now, the present invention will be described with reference to drawings.

In this specification, abbreviated names of halogenated hydrocarboncompounds are described in brackets after the compound names, and theabbreviated names are employed instead of the compound names as the caserequires. Further, as abbreviated names, only numerals and smallalphabet letters after a hyphen (-) (for example, “1224yd” in the caseof “HCFO-1224yd”) may be used.

Further, (E) before the compound name or after its abbreviated name of acompound having cis-trans isomers represents an E-form (trans-isomer)and (Z) represents a Z-form (cis-isomer). The compound name or theabbreviated name without description of E or Z generally means E-form,Z-form and a mixture of E-form and Z-form.

In this specification, evaluation of “combustibility” is based on thefollowing standards.

In combustion test carried out with respect to a mixture of a specimenand air in a container controlled at 60° C.±3° C. under 101.3 kPa±0.7kPa in facilities as specified in ASTM E-681-09, when the mixture has nocombustibility in the entire range of a proportion of the specimen tothe total volume of the mixture being higher than 0 vol % and up to 100vol %, such a specimen is evaluated to “have no combustibility”. Thewording “incombustible” is synonymously used with the wording “having nocombustibility”. When a mixture of a specimen and air has combustibilityin any proportion, such a specimen is evaluated to “have combustibility”or to “have a combustible range”.

In the combustion test, in a gaseous phase in the vicinity of the centerof the container, a fire is made by discharge ignition under 15 kV at 30mA for 0.4 second, spread of flame is visually confirmed, and when theangle of spread of the flame upward is at least 90 degrees, such aspecimen is evaluated to have combustibility, and when the angle is lessthan 90 degrees, such a specimen is evaluated to have no combustibility.

In this specification, GWP is a value (100 years) in IntergovernmentalPanel on Climate Change (IPCC), Fifth assessment report (2014), or avalue measured in accordance therewith. Further, GWP of a mixture isrepresented by a weighted average by the composition mass.

In this specification, “spraying” means that a content including apropellant composition filled in the interior of a sprayer is sprayedfrom the interior of the sprayer to the outside by the propellantcomposition in a liquid state, a gaseous state, a solid state or a mixedstate thereof.

FIGS. 1A and 1B are schematic views illustrating a use example of oneexample of a one component type of the sprayer of the present invention.FIGS. 2A and 2B are schematic views illustrating a use example of oneexample of a two component type of the sprayer of the present invention.

In FIG. 1A, a sprayer 10 comprises a container 1, a propellantcomposition X_(I) containing 1224yd contained in the interior of thecontainer 1, and a spray unit 2 to spray the propellant compositionX_(I) to the outside of the container. The container 1 has anaccommodating portion 12 and an opening 11. The spray unit 2 is attachedto the opening 11 of the container 1, and has a function to seal theinterior of the container 1. The accommodating portion 12 of thecontainer 1 is filled with the propellant composition X_(I), and thepropellant portion X_(I) consists of a liquid phase portion L_(I) and agaseous phase portion G_(I).

The spray unit 2 has an inlet 22 facing the accommodating portion 12,and has a mechanism to bring in the gaseous phase portion G_(I) of thepropellant composition X_(I) in the accommodating portion 12 into theinterior of the spray unit 2 from the inlet 22. The spray unit 2 has aspray nozzle 21 provided so as to face the outside of the container 1and connected to the inlet 22 via a flow path in the interior of thespray unit 2. The spray unit 2 has a mechanism to spray the gaseousphase portion G_(I) of the propellant composition X_(I) brought into theinterior of the spray unit 2 to the outside of the container 1 from thespray nozzle 21.

FIGS. 1A and 1B illustrate a state where the gaseous phase portion G_(I)of the propellant composition X_(I) is sprayed from the sprayer 10.After the sprayer sprayed a required amount of the propellantcomposition at the time of use, it is stored in a sealed state, and itsuse may be completed after spraying of the propellant composition isrepeated several times, or its use may be completed after spraying once.The spray unit has a function to spray the propellant composition to theoutside of the sprayer at the time of use, and has a function to keep asealed state of the sprayer when not used, and for example, switching isconducted by opening/closing of a valve.

Spraying of the gaseous phase portion G_(I) of the propellantcomposition X_(I) from the spray unit 2 is conducted utilizing apressure of the propellant composition X_(I) filled in the accommodatingportion 12 of the container 1.

FIG. 1A illustrates a use example at an initial stage of use of thesprayer 10, and FIG. 1B illustrates a use example at a last stage of useof the sprayer 10. At the initial stage of use, the volume of the liquidphase portion L_(I) of the propellant composition X₁ filled in theaccommodating portion 12 of the container 1 is large as compared withthe volume of the gaseous phase portion G_(I). The liquid phase portionL_(I) and the gaseous phase portion G_(I) are in a gas-liquidequilibrium state. The sprayer 10 sprays the gaseous phase portion G_(I)of the propellant composition X_(I) from the spray unit 2 at the time ofuse, accompanied by vaporization of the liquid phase portion in anamount corresponding to the decreased gaseous phase portion to newlyform a vapor-liquid equilibrium state in the accommodating portion 12 ofthe container 1. In such a manner, along with use of the sprayer 10, thevolume of the liquid phase portion decreases in the accommodatingportion 12 of the container, and the volume of the gaseous phase portionincreases, and finally, the pressure in the interior of the container 1in the sprayer 10 becomes equal to the pressure of the outside of thecontainer 1, usually atmospheric pressure (=0.1013 MPa), and use of thesprayer is completed.

In the sprayer 10, by use of the sprayer, that is, along with sprayingof the propellant composition to the outside, the liquid phase portionin the accommodating portion 12 in the container 1 is consumed and as aresult, the pressure in the interior of the container 1 becomes equal tothe pressure of the outside of the container 1, usually atmosphericpressure, whereby the use may be completed, or the pressure in theinterior of the container 1 becomes equal to the pressure of the outsideof the container 1, usually atmospheric pressure, in a state where theliquid phase portion remains in the accommodating portion 12 of thecontainer 1, whereby the use may be completed.

FIG. 1B illustrates a use example of the last stage of use of thesprayer 10. In the sprayer 10 at this stage, the volume of the liquidphase portion L_(L) of the propellant composition X_(L) filled in theaccommodating portion 12 of the container 1 is small as compared withthe volume of the gaseous phase portion G_(L).

In the sprayer 10 shown in FIG. 1A, in a case where the propellantcomposition X₁ is constituted solely by 1224yd, the compositions of theliquid phase portions L_(I) and the gaseous phase portion G_(I) are thesame with 100 mass % of 1224yd. Further, in a case where the propellantcomposition X_(I) is an azeotropic composition which is a mixture of twoor more types of compounds containing 1224yd, the compositions of theliquid phase portion L_(I) and the gaseous phase portion G_(I) are thesame. And, also in the sprayer 10 shown in FIG. 1B at the last stage ofuse, there is no difference in the composition between the liquid phaseportion L_(L) and the gaseous phase portion G_(L), and further, thesecompositions have no difference in the compositions of the liquid phaseportion L_(I) and the gaseous phase portion G_(I) at the initial stageof use.

On the other hand, in a case where the propellant composition X_(I)filled in the sprayer 10 is a non-azeotropic composition which is amixture of two or more types of compounds containing 1224yd, thecomposition of the liquid phase portion L_(I) and the composition of thegaseous phase portion G_(I) of the propellant composition X_(I) aredifferent from each other at the initial stage of use. And, along withuse of the sprayer 10, the gas-liquid equilibrium of the liquid phaseportion and the gaseous phase portion of the propellant composition inthe accommodating portion 12 of the container 1 varies. Accordingly, inthe sprayer 10 shown in FIG. 1B at the last stage of use, thecompositions of the liquid phase portion L_(L) and the gaseous phaseportion G_(L) are different from each other, and further, thecompositions of the liquid phase portion L_(L), the gaseous phaseportion G_(L), the liquid phase portion L_(I) and the gaseous phaseportion G_(I) at the initial stage of use are different from oneanother.

In FIG. 2A, a sprayer 20 comprises a container 1, a propellantcomposition X₁ containing 1224yd contained in the interior of thecontainer 1, and a spray unit 2 to spray the propellant compositionX_(I) to the outside of the container 1. In the sprayer 20, in theinterior of the container 1, a chemical agent E is contained togetherwith the propellant composition X_(I), and the propellant composition X₁is sprayed together with the chemical agent E by the spray unit 2 to theoutside of the container 1. The container 1 has an accommodating portion12 and an opening 11. The sprayer 2 is attached to the opening 11 of thecontainer 1, and has a function to seal the interior of the container 1.The accommodating portion 12 of the container 1 is filled with thepropellant composition X_(I) and the chemical agent E. The propellantcomposition X_(I) consists of a liquid phase portion L_(I) and a gaseousphase portion G_(I), and the chemical agent E is present in a liquidmixture with the liquid phase portion L_(I). That is, the interior ofthe accommodating portion 12 of the container 1 is filled with a liquidmixture of the chemical agent E and the liquid phase portion L_(I) ofthe propellant composition X_(I), and the gaseous phase portion G_(I) ofthe propellant composition X_(I).

The spray unit 2 has a nozzle 23 which extends to the bottom of theaccommodating portion 12 of the container 1, and has a mechanism tobring the liquid mixture of the chemical agent E and the liquid phaseportion L_(I) of the propellant composition X₁ in the accommodatingportion 12 from the tip of the nozzle 23 into the interior of the sprayunit 2 via the nozzle 23. The spray unit 2 has a spray nozzle 21provided so as to face the outside of the container 1 and connected tothe nozzle 23 via a flow path in the interior of the spray unit 2. Thespray unit 2 has a mechanism to spray the liquid mixture of the chemicalagent E and the liquid phase portion L_(I) of the propellant compositionX_(I) brought into the interior of the spray unit 2 to the outside ofthe container 1 from the spray nozzle 21.

FIGS. 2A and 2B illustrate a state where the liquid mixture of thechemical agent E and the liquid phase portion L_(I) of the propellantcomposition X_(I) is sprayed from the sprayer 20. In the sprayer 20also, the spray unit has, in the same manner as the sprayer 10, afunction to spray the liquid mixture to the outside of the sprayer atthe time of use and a function to keep a sealed state of the sprayerwhen not used, and for example, switching is conducted byopening/closing of a valve.

Spraying of the liquid mixture of the chemical agent E and the liquidphase portion L_(I) of the propellant composition X_(I) from the sprayunit 2 is conducted by utilizing the pressure of the propellantcomposition X_(I) filled in the accommodating portion 12 of thecontainer 1.

FIG. 2A illustrates a use example at an initial stage of use of thesprayer 20, and FIG. 2B illustrates a use example at a last stage of useof the sprayer 20. At the initial stage of use, in the accommodatingportion 12 of the container 1, the volume of the liquid mixture of thechemical agent E and the liquid phase portion L_(I) of the propellantcomposition X_(I) is large as compared with the volume of the gaseousphase portion G_(I) of the propellant composition X_(I). The liquidphase portion L_(I) and the gaseous phase portion G_(I) of thepropellant composition X_(I) are in a gas-liquid equilibrium state.

The sprayer 20 sprays the liquid mixture of the chemical agent E and theliquid phase portion L_(I) of the propellant composition X_(I) from thespray unit 2 at the time of use, accompanied by vaporization of theliquid phase portion of the propellant composition to compensate for theconsumed volume of the liquid mixture, to newly form a gas/liquidequilibrium state in the liquid phase portion and the gaseous phaseportion of the propellant composition, in the accommodating portion 12of the container 1. In such a manner, along with use of the sprayer 20,in the accommodating portion 12 of the container 1, the volume of theliquid mixture decreases and in addition, the volume of the gaseousphase portion consisting of the propellant composition increases andfinally, the pressure of the interior of the container 1 in the sprayer20 becomes equal to the pressure of the outside of the container 1,usually atmospheric pressure, whereby use of the sprayer is completed.

In the sprayer 20 also, in the same manner as the sprayer 10, along withuse of the sprayer, the liquid phase portion in the accommodatingportion 12 of the container 1 is consumed and as a result, the pressureof the interior of the container 1 becomes equal to the pressure of theoutside of the container 1, usually atmospheric pressure, whereby theuse may be completed, or the pressure of the interior of the container 1becomes equal to the pressure of the outside of the container 1, usuallyatmospheric pressure, in a state where the liquid phase portion remainsin the accommodating portion 12 of the container 1, whereby the use maybe completed.

FIG. 2B illustrates a use example at the last stage of use of thesprayer 20. In the sprayer 20 at this stage, in the accommodatingportion 12 of the container 1, the volume of the liquid mixture of thechemical agent E and the liquid phase portion L_(I) of the propellantcomposition X₁ is small as compared with the volume of the gaseous phaseportion G_(I) of the propellant composition X_(I).

In the sprayer 20, in the same manner as the sprayer 10, in a case wherethe propellant composition X₁ is constituted solely by 1224yd or is anazeotropic composition, there is no difference in the compositionbetween the liquid phase portion L_(I) and the gaseous phase portionG_(I) at the initial stage of use and the liquid phase portion L_(L) andthe gaseous phase portion G_(L) at the last stage of use. However, in acase where the propellant composition X₁ is a mixture of two or moretypes of compounds containing 1224yd and is a non-azeotropiccomposition, all the compositions of the liquid phase portion L_(I) andthe gaseous phase portion G_(I) at the initial stage of use and theliquid phase portion L_(L) and the gaseous phase portion G_(L) at thelast stage of use are different.

In the sprayer of the present invention, the propellant composition tobe sprayed satisfies the following requirements (1) and (2) throughoutthe entire period over which the sprayer is used:

(1) the propellant composition is incombustible.

(2) GWP is less than 10.

“Throughout the entire period over which the sprayer is used” means theentire period from the start of use of the sprayer until the pressure inthe sprayer becomes equal to the pressure of the outside of the sprayer.The pressure of the outside of the sprayer is usually atmosphericpressure.

In the one component type sprayer 10, the propellant composition to besprayed is the gaseous phase portion G_(I) of the propellant compositionX_(I) filled in the accommodating portion 12 of the container 1. Inorder that the propellant composition to be sprayed from the sprayer 10satisfies the requirement (1) throughout the entire period over whichthe sprayer is used, the gaseous phase portion of the propellantcomposition in the accommodating portion 12 of the container 1 should beincombustible from the gaseous phase portion G_(I) at the initial stageof use via the gaseous phase portion G_(L) to the last stage of use.When the propellant composition to be sprayed from the sprayer 10satisfies the requirement (1) throughout the entire period over whichthe sprayer is used, the propellant composition has no combustibilityeven when mixed with air at any proportion as the gaseous phase portionG_(I) or the gaseous phase portion G_(L) is diffused to the outside ofthe container and diluted with air, and has high safety, as shown inFIGS. 1A and 1B.

In the two component type sprayer 20, the propellant composition to besprayed is the liquid mixture of the chemical agent E and the liquidphase portion L_(I) of the propellant composition X_(I) in theaccommodating portion 12 of the container 1. The liquid phase portionL_(I) of the propellant composition X_(I) in the liquid mixture isvaporized when sprayed and becomes gaseous phase GL_(I) with nodifference in the composition with the liquid phase portion L_(I). Inorder that the propellant composition to be sprayed from the sprayer 20satisfies the requirement (1) throughout the entire period over whichthe sprayer is used, the liquid phase portion of the propellantcomposition in the accommodating portion 12 of the container 1 should beincombustible from the liquid phase portion L_(I) at the initial stageof use via the liquid phase portion L_(L) to the last stage of use. Whenthe propellant composition to be sprayed from the sprayer 20 satisfiesthe requirement (1), the propellant composition has no combustibilityeven when mixed with air at any proportion as the gaseous phase portionGL_(I) or the gaseous phase portion GL_(L) together with the chemicalagent E is diffused to the outside of the container and diluted withair, and has high safety, as shown in FIGS. 2A and 2B.

In a case where the propellant composition is constituted solely by1224yd, since 1224yd is incombustible as shown hereinafter, thepropellant composition to be sprayed satisfies the requirement (1) forthe sprayer throughout the entire period over which the sprayer is used.However, in a case where the propellant composition is a non-azeotropiccomposition containing 1224yd, in order that the propellant compositionto be sprayed satisfies the requirement (1) for the sprayer throughoutthe entire period over which the sprayer is used, the initialcomposition of the propellant composition is determined considering theabove-described composition change of the propellant composition to besprayed.

Further, in a case where the propellant composition is constitutedsolely by 1224yd, GWP of 1224yd is 1, and the propellant composition tobe sprayed satisfies the requirement (2) for the sprayer throughout theentire period over which the sprayer is used. GWP in a case where thepropellant composition is a mixture is a weighted average by thecomposition mass. In order that the propellant composition to be sprayedsatisfies the requirement (2) for the sprayer throughout the entireperiod over which the sprayer is used, the initial composition of thepropellant composition is determined considering the above-describedcomposition change of the propellant composition to be sprayed.

Further, in addition to that the propellant composition to be sprayedsatisfies the above requirements (1) and (2) throughout the entireperiod over which the sprayer is used, the propellant composition isadjusted preferably so that the pressure in the container is within arange specified by High Pressure Gas Safety Act, that is, at most 0.8MPaG (=0.9013 MPa) at 35° C. “G” in the pressure unit represents gagepressure. Now, the propellant composition used for the sprayer of thepresent invention will be described.

[Propellant Composition]

The propellant composition contains 1224yd, and is adjusted so that thepressure in the container of the sprayer in which the propellantcomposition is contained is higher than the pressure of the outside ofthe sprayer, and so that the propellant composition to be sprayedsatisfies the requirements (1) and (2) throughout the entire period overwhich the sprayer is used.

(1224yd)

1224yd(CF₃—CF═CHCl) has halogen to suppress combustibility and acarbon-carbon double bond which is easily decomposable by OH radicals inthe air, in its molecule. 1224yd has cis-trans isomers 1224yd(Z) and1224yd(E). 1224yd(Z) has a boiling point of 15° C., and 1224yd(E) has aboiling point of 19° C. GWP of 1224yd(Z) is 1, and GWP of 1224yd(E) is<1. 1224yd(Z) has high chemical stability as compared with 1224yd(E).

1224yd(Z), 1224(E) and a mixture thereof, that is, 1224yd areincombustible.

1224yd used for the propellant composition according to the presentinvention has a proportion of 1224yd(Z) to the total amount of 1224yd ofpreferably from 50 to 100 mass %, more preferably from 80 to 100 mass %,further preferably from 90 to 100 mass %, still more preferably from 99to 100 mass %, from the viewpoint of chemical stability.

As a method for producing 1224yd, for example, (I) a method ofsubjecting 1,2-dichloro-2,3,3,3-tetrafluoropropane (HCFC-234bb) todehydrochlorination reaction, or (II) a method of subjecting1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) to hydrogenreduction may, for example, be mentioned.

In each production method, the product to be obtained is usually a1224yd composition containing 1224yd(Z), 1224yd(E) and impurities otherthan 1224yd. It is possible to produce 1224yd(Z) and 1224yd(E) bypurifying the obtained 1224yd composition. However, in order to obtainpure 1224yd(Z) and 1224yd(E), separation with high purity using a highperformance separation apparatus is required, thus lowering theproductivity. In the propellant composition of the present invention,from the viewpoint of production efficiency, within a range not toimpair the effects of the present invention, the 1224yd compositioncontaining as impurities a compound other than 1224yd resulting fromproduction of 1224yd, may be used.

Further, particularly when 1224yd(Z) among 1224yd is used for thepropellant composition, in the same manner as above, from the viewpointof production efficiency, within a range not to impair the effects ofthe present invention, a 1224yd(Z) composition containing as impuritiesa compound other than 1224yd(Z) may be used.

(I) Dehydrochlorination reaction of 234bb 234bb is brought into contactwith a base dissolved in a solvent, that is, a base in a solution state,in a liquid phase, to conduct dehydrochlorination reaction of 234bb.234bb may be produced, for example, by reacting 1234yf and chlorine in asolvent.

The compound other than 1224yd contained in the 1224yd compositionobtained by the method (I) may be 234bb which is an unreacted rawmaterial, and 1234yf, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe),1214ya, 1,1,2-trichloro-2,3,3,3-tetrafluoropropane (CFC-224ba),1,1,1,2-tetrachloro-2,3,3,3-tetrafluoropropane (CFC-214bb),1-chloro-3,3,3-trifluoro-1-propine and2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and the like.

234bb, 1214ya, 224ba, 214bb, etc. in the 1224yd composition can be morecompletely removed by a purification method to such an extent not toimpair the productivity. On the other hand, 1234yf, 1224xe,1-chloro-3,3,3-trifluoro-1-propine and 244bb may not be completelyremoved in the purification method and they may remain in a very smallamount, for example, in an amount of less than 1.5 mass % in total tothe total amount of the obtained 1224yd composition.

Further, for example, in the 1224yd(Z) composition, 1224yd(E) is one ofcomponents which cannot completely be removed by the purification methodand remain in a very small amount. That is, in the 1224yd(Z)composition, 1224yd(E) may remain in an amount of less than 1.5 mass %in total of 1234yf, 1224xe, 1-chloro-3,3,3-trifluoro-1-propine, 244bband 1224yd(E) to the total amount of the obtained 1224yd(Z) composition.

Among the above trace components in the 1224yd composition, 1224xe and1-chloro-3,3,3-trifluoro-1-propine, and in the case of the 1224yd(Z)composition, 1224yd(E) in addition to the above, are incombustible andhave GWP of less than 10, and accordingly they may remain and becontained in the propellant composition in a total amount of less than1.5 mass %.

Among the above trace components, 1234yf has GWP of 1 but has acombustible range. As described hereinafter, 1234yf is a componentpreferably used for the propellant composition in combination with1224yd, and the composition with 1224yd will be described hereinafter.

As described above, in the 1224yd composition and the 1224yd(Z)composition containing the above compounds as impurities in a totalamount of less than 1.5 mass % to the total amount of the composition,the impurities will not impair the effects of the present invention, andsuch a composition may be used as the propellant composition of thepresent invention.

(II) Method of Subjecting 1214ya to Hydrogen Reduction

1214ya is reduced using hydrogen in the presence of a catalyst so as tobe converted to 1234yf, and 1224yd is obtained as an intermediate. Bythis reduction reaction, a variety of fluorinated compounds are formedas by-products in addition to 1224yd. 1214ya is produced, for example,by a method of subjecting 3,3-dichloro-1,1,1,2,2-pentafluoropropane(HCFC-225ca) and the like as raw materials to dehydrofluorinationreaction in an alkaline aqueous solution in the presence of a phasetransfer catalyst, or by a gaseous phase reaction in the presence of acatalyst such as chromium, iron, copper or activated carbon.

In such a case, 1224yd may be separated from the most part of 1214ya asan unreacted raw material and 1234yf as a final product, by conventionaldistillation.

Compounds other than 1224yd contained in the 1224yd composition afterdistillation obtained by the above method (II) may, for example, be1,1,1,2-tetrafluoropropane (HFC-254eb),2-chloro-1,1,3,3,3-pentafluoropropene (CFO-1215xc),1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1234ze, fluorinatedhydrocarbon represented by C₄H₄F₄,1-chloro-1,2,2,3,3,3-hexafluoropropane (HCFC-226ca),1-chloro-1,1,2,2,3,3-hexafluoropropane (HCFC-226cb),1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb),1,1,2,3-tetrafluoropropane (HFC-254ea),2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba), 1224xe, 1214ya,1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb),1,2-dichloro-1,3,3,3-tetrafluoropropene (CFO-1214xb), 244bb,1,1,1,3,3-pentafluoropropane (HFC-245fa), 225ca and1,1,1,2,2,3,3-heptafluoropropane (FC-227ca).

The fluorinated hydrocarbon represented by C₄H₄F₄ may, for example, be1,3,4,4-tetrafluoro-1-butene, 3,4,4,4-tetrafluoro-1-butene or1,1,2,3-tetrafluoro-1-butene.

The impurities contained in the 1224yd composition form an azeotropiccomposition or an azeotrope-like composition with 1224yd, andaccordingly a purification method by extractive distillation iseffective as a purification method to obtain a purified composition.Extractive distillation is a method to facilitate separation bydistillation by adding another component to a composition comprising aplurality of components to change the relative volatility of thepredetermined component, and another component here will be referred toas an extraction solvent. The extraction solvent for 1224yd may, forexample, be methanol, acetone, hexane, ethanol, 1214ya, chloroform, and1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb).

By the above purification treatment, among the above impurities, 236fa,226ca, 226cb, 1224zb, 254ea, 226ba, 1214ya, 1214yb, 1214xb, etc. arecompletely removed from the crude composition. On the other hand, in the1224yd composition, 1215xc, 254eb, 1234ze, the fluorinated hydrocarbonrepresented by C₄H₄F₄, 1224xe, 244bb, 245fa, 225ca and 227ca cannot becompletely removed by the purification treatment and remain in a verysmall amount. Further, methanol, acetone, hexane, ethanol, 1214ya,chloroform, 225cb, etc. used as the extraction solvent may remain in avery small amount. Their total amount is, for example, preferably lessthan 1.5 mass % to the total amount of the 1224yd composition obtained.

Even in such a case, in the 1224yd(Z) composition, in addition to theabove impurities, 1224yd(E) is one of components which cannot completelybe removed by the purification method and remain in a very small amount.

Among the above trace components, 1234ze has GWP of 1 but has acombustible range. As described hereinafter, 1234ze is a componentpreferably used for the propellant composition in combination with1224yd, and the composition with 1224yd will be described hereinafter.

As described above, in the 1224yd composition and the 1224yd(Z)composition containing the above compounds as impurities in a totalamount of less than 1.5 mass % to the total amount of the composition,the impurities will not impair the effects of the present invention, andsuch compositions may be used as the propellant composition of thepresent invention.

(Propellant Component Other than 1224yd)

In the present invention, the propellant composition contains 1224yd.The propellant composition may contain a propellant component other than1224yd within a range where the propellant composition can make thepressure in the container of the sprayer filled with the propellantcomposition higher than the pressure of the outside of the sprayer,usually atmospheric pressure, and the propellant composition to besprayed satisfies the above requirements (1) and (2) throughout theentire period over which the sprayer is used.

The propellant component other than 1224yd is preferably ahydrofluoroolefin (HFO). The most of HFOs have GWP of less than 10, andan incombustible HFO may constitute a propellant composition freely incombination with 1224yd as the case requires. The HFO is specificallypreferably 1234yf, 1234ze or 1336mzz. The HFO may be used alone or incombination of two or more.

Among HFOs, 1234yf and 1234ze have a combustible range but have GWP of1, have a lower boiling point than 1224yd, and can increase the pressureof the propellant composition X_(I) in the accommodating portion 12 ofthe container 1.

A propellant composition comprising a combination of 1224yd and 1234yfor 1234ze to be sprayed satisfies the requirement (2) throughout theentire period over which the sprayer is used, in any composition. Withrespect to the propellant composition comprising a combination of 1224ydand 1234yf or 1234ze, the initial composition in order that thepropellant composition to be sprayed satisfies the requirement (1)throughout the entire period over which a one component type sprayerfrom which the gaseous phase portion in the container is sprayed, isdetermined, for example, as follows.

(i) Condition setting is carried out. The conditions are the temperatureand the volume ratio of the liquid phase portion and the gaseous phaseportion of the propellant composition in the accommodating portion ofthe container at an initial state.

(ii) The initial composition of the propellant composition to beintroduced to the accommodating portion of the container is set.

(iii) Whether or not the propellant composition (gaseous phase portion)to be sprayed satisfies the requirement (1) from the beginning to theend (the vapor pressure of the liquid phase portion becomes atmosphericpressure) when kept being sprayed at the constant temperature isconfirmed.

(iv) Back to (ii), the initial composition is changed.

(v) (ii) to (iv) are repeatedly carried out until the initialcomposition range within which the propellant composition (gaseous phaseportion) sprayed in (iii) satisfies the requirement (1) from thebeginning to the end, is found.

The composition change of the liquid phase portion and the gaseous phaseportion during the use period in (iii) is carried out by calculation.Physical properties of 1224yd used for the calculation were calculatedbased on physical properties described in Akasaka, R., Fukushima, M.,Lemmon, E. W., “A Helmholtz Energy Equation of State forcis-1-chloro-2,3,3,3-tetrafluoropropene (R-1224yd(Z))”, EuropeanConference on Thermophysical Properties, Graz, Austria, Sep. 3-8, 2017.Physical properties of compounds other than 1224yd were calculated basedon physical values of REFPROP ver. 9.1 of NIST (National Institute ofStandards and Technology). The composition change was calculated byusing REFLEAK ver. 4.0 of NIST (National Institute of Standards andTechnology).

According to the above setting method, for example, with respect to thepropellant composition comprising 1224yd(Z) and 1234ze(E), in a casewhere the volume ratio of the liquid phase portion and the gaseous phaseportion of the propellant composition in the accommodating portion ofthe container at 10° C. at an initial state, is such that the liquidphase portion is 90 vol %, the requirement (1) is satisfied when theproportion of the content of 1224yd(Z) is at least 42 mass % and lessthan 100 mass % and the proportion of the content of 1234ze(E) is higherthan 0 mass % and at most 58 mass %, to the total amount of 1224yd(Z)and 1234ze(E) in the propellant composition. Further, from the viewpointof spraying properties, the proportion of the content of 1224yd(Z) ispreferably at least 42 mass % and at most 63 mass %, and the proportionof the content of 1234ze(E) is preferably at least 37 mass % and at most58 mass %.

According to the above setting method, with respect to the propellantcomposition comprising 1224yd(Z) and 1234yf, in a case where the volumeratio of the liquid phase portion and the gaseous phase portion of thepropellant composition in the accommodating portion of the container at10° C. at an initial state, is such that the liquid phase portion is 90vol %, the requirement (1) is satisfied when the proportion of thecontent of 1224yd(Z) is at least 67 mass % and less than 100 mass % andthe proportion of the content of 1234yf is higher than 0 mass % and atmost 33 mass %, to the total amount of 1224yd(Z) and 1234ze(E) in thepropellant composition. Further, from the viewpoint of sprayingproperties, the proportion of the content of 1224yd(Z) is preferably atleast 67 mass % and at most 77 mass %, and the proportion of the contentof 1234ze(E) is preferably at least 23 mass % and at most 33 mass %.

In each of the propellant composition comprising 1224yd(Z) and 1234ze(E)and the propellant composition comprising 1224yd(Z) and 1234yf, theconcentration of 1234ze(E) or 1234yf in the gaseous phase portion ishigh as compared with the liquid phase portion, since the boiling pointsof 1234ze(E) (boiling point: −19° C.) and 1234yf (boiling point: −29.4°C.) are low as compared with 1224yd(Z). Accordingly, the concentrationof 1234ze(E) or 1234yf in the gaseous phase portion decreases along withuse, and thus when the propellant composition (gaseous phase portion)sprayed at the beginning is incombustible in (iii), such a propellantcomposition can be considered to be incombustible to the end.

That is, the propellant composition comprising 1224yd(Z) and 1234ze(E)to be sprayed is incombustible throughout the entire period over whichthe sprayer is used when the proportion of the content of 1224yd(Z) isat least 20 mass % and less than 100 mass % and the proportion of thecontent of 1234ze(E) is higher than 0 mass % and at most 80 mass %, tothe total amount of 1224yd(Z) and 1234ze(E) in the gaseous phase portionof the propellant composition when filled so that the liquid phaseportion in the container is 90 vol %. Further, the propellantcomposition comprising 1224yd(Z) and 1234yf to be sprayed isincombustible throughout the entire period over which the sprayer isused when the proportion of the content of 1224yd(Z) is at least 30 mass% and less than 100 mass % and the proportion of the content of 1234yfis higher than 0 mass % and at most 70 mass %, to the total amount of1224yd(Z) and 1234yf in the gaseous phase portion of the propellantcomposition when filled so that the liquid phase portion in thecontainer is 90 vol %.

Further, with respect to a two component type sprayer from which theliquid phase portion in the container is sprayed, the initialcomposition so that the propellant composition (1) to be sprayedsatisfies the requirement (1) throughout the entire period over whichthe sprayer is used, may be obtained, for example, by conducting thesame calculation changing the propellant composition to be sprayed in(iii) from the gaseous phase portion to the liquid phase portion.

Further, the same calculation as above may be applicable even when thetemperature condition or the volume ratio of the liquid phase portionand the gaseous phase portion of the propellant composition in theinitial accommodating portion is changed. Further, the same calculationmay be applicable also in a case where the compound to be combined ischanged.

(Other Component)

The propellant composition may optionally contain components other thanthe above propellant components. The propellant composition may contain,as other component, for example, a pressurizing agent. The pressurizingagent may, for example, be specifically nitrogen, carbon dioxide or aninert gas. The inert gas may, for example be helium, argon, krypton,xenon or radon.

The propellant composition may further contain a known additive such asa lubricant or a stabilizer. The stabilizer is a component whichimproves the stability of the propellant component against heat andoxidation. As the stabilizer, a known stabilizer which has been used fora propellant composition containing a halogenated hydrocarbon, forexample, an oxidation resistance-improving agent, a heatresistance-improving agent and a metal deactivator may be used withoutany particular restriction. For the propellant composition to be used inthe present invention, particularly a stabilizer to improve thestability of 1224yd is preferred.

The oxidation-resistance improving agent and the heatresistance-improving agent may, for example, be a phenol compound, anunsaturated hydrocarbon group-containing aromatic compound, an aromaticamine compound, an aromatic thiazine compound, a terpene compound, aquinone compound, a nitro compound, an epoxy compound, a lactonecompound, an orthoester compound, a mono- or dialkali metal salt ofphthalic acid, or a thiodiphenyl ether hydroxide compound.

Further, the metal deactivator may be a heterocyclic nitrogen-containingcompound such as an imidazole compound, a thiazole compound or atriazole compound, an amine salt of an alkyl acid phosphate or itsderivative.

The content of the stabilizer may be within a range not to remarkablyimpair the effects of the present invention, and is preferably from 1mass ppm to 10 mass %, more preferably from 5 mass ppm to 5 mass % inthe propellant composition (100 mass %).

(Impurities in Propellant Composition)

The sprayer is usually stored for a predetermined time from itsproduction until its use. Accordingly, there may be problems if thepropellant composition contains the after-described impurities in apredetermined amount or more. The amount of each impurity is preferablyat most a predetermined amount.

<Acid Content>

If an acid content is present in the propellant composition, it hasadverse effects such as decomposition of the propellant component. Theconcentration of the acid content in the propellant composition is, asthe concentration by acid-alkali titration method, preferably less than1 mass ppm, particularly preferably at most 0.8 mass ppm. Theconcentration of a predetermined component in the propellant compositionmeans a mass proportion of the content of the component to the totalamount of the propellant composition.

<Moisture>

If moisture is included in the propellant composition, problems such ashydrolysis of the propellant component, material deterioration by anacid component generated in the container, and contaminants may arise.The moisture content in the propellant composition is, as the moisturecontent measured by Karl Fischer coulometric titration method,preferably at most 20 mass ppm, particularly preferably at most 15 massppm to the total amount of the propellant composition.

<Air>

If air (nitrogen: about 80 vol %, oxygen: about 20 vol %) is included inthe propellant composition, it has adverse effects over the performanceof the propellant composition, and accordingly it is necessary toprevent inclusion of air as far as possible. Particularly, oxygen in airreacts with the propellant component and promotes its decomposition. Theair concentration in the propellant composition is, as the airconcentration measured by gas chromatography, preferably less than15,000 mass ppm, particularly preferably at most 8,000 mass ppm.

(Chemical Agent)

In a case where the sprayer of the present invention is a two componenttype, a chemical agent is sealed together with the propellantcomposition in the container. As the chemical agent, a chemical agentknown as a chemical agent used together with the propellant compositionfor a two component type sprayer may be used without any particularrestriction. The chemical agent may, for example, be a cleaning agent, afungicide, a coating material, a deodorant, a waterproof agent, adisinfectant, an evaporative cooling agent, a hair dye, apharmaceutical, an anticorrosive agent, an anti-fouling agent, ananti-fogging agent, a lubricant, a release agent, anelectrostatic/antistatic agent, an extreme-pressure agent, a penetratingagent and an adhesive.

(Method for Producing Sprayer)

As the member constituting the sprayer of the present invention, amember constituting a known sprayer, for example, a container and aspray unit may be used without any particular restriction, except thatthe above propellant composition containing 1224yd is used as thepropellant composition. As the production method also, known productionmethods corresponding to the one component type and the two componenttype may be applicable.

The embodiments of the sprayer of the present invention were describedabove, however, the sprayer of the present invention is not limited tothe above embodiments. Various changes and modifications are possiblewithout departing from the intention and the scope of the presentinvention.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific description.

(Combustion Test)

Combustibility was evaluated with respect to compositions comprising1224yd(Z) and 1234ze(E) in Test Examples 1 to 4, compositions comprising1224yd and 1234yf in Test Examples 5 to 8, 1224yd(Z) in Test Example 9,1234ze(E) in Test Example 10 and 1234yf in Test Example 11, asidentified in Table 1.

Evaluation of combustibility was carried out using a measuring apparatusas specified in ASTM E681-09. The interior of a round flask having aninternal capacity of 12 liter controlled to a temperature of 60±3° C.was evacuated of air, and each composition, dry air and moisture weresealed until the pressure in the flask became 101.3 kPa±0.7 kPa. Then, afire was made by discharge ignition under 15 kV at 30 mA for 0.4 secondby electrodes disposed at a height of one third from the bottom of theflask, and spread of flame was visually confirmed. The amount of themoisture was 0.0088 g±0.0005 g per 1 g of dry air. The mixing ratio ofeach composition to dry air was changed by changing the amount of thecomposition sealed every 1.0 vol %±0.2 vol %, and whether thecomposition has combustibility or not was confirmed. When the angle ofspread of the flame upward was at least 90 degrees, the composition wasevaluated to have combustibility (combustible), and when the angle wasless than 90 degrees, the composition was evaluated to have nocombustibility (incombustible). The results are shown in Table 1.

Test Composition [mass%] Example 1224yd(Z) 1234ze(E) 1234yfCombustibility 1 40 60 Incombustible 2 30 70 Incombustible 3 20 80Incombustible 4 10 90 Combustible 5 50 50 Incombustible 6 40 60Incombustible 7 30 70 Incombustible 8 20 80 Combustible 9 100  — —Incombustible 10  — 100  — Combustible 11  — — 100  Combustible

It was found from Table 1 that the composition comprising 1224yd(Z) and1234ze(E) is incombustible when it has a proportion of the content of1224yd(Z) of at least 20 mass % to the total amount of 1224yd(Z) and1234ze(E). It was found that the composition comprising 1224yd(Z) and1234yf is incombustible when it has a proportion of the content of1224yd(Z) of at least 30 mass % to the total amount of 1224yd(Z) and1234yf.

(Spray Test) Example 1

Under temperature conditions of 10±3° C., a propellant compositioncomprising 1224yd(Z) and 1234ze(E) and having a content of 1224yd(Z) of42 mass % and a content of 1234ze(E) of 58 mass % was filled in apressure container so that 90 vol % of the propellant composition was ina liquid phase, and a valve as a spray unit was attached to the upperpart of the pressure container to prepare a one component type sprayer.Using the sprayer, the following spray test was carried out in which thevalve was opened to spray the gaseous phase of the propellantcomposition in the pressure container. The spray test was conductedentirely under temperature conditions of 10±3° C.

The pressure (kPa) in the pressure container at an initial state filledwith the propellant composition (GWP: 1), the compositions of the liquidphase and the gaseous phase of the propellant composition, and thecombustibility were obtained. Then, the pressure in the pressurecontainer, the compositions of the liquid phase and the gaseous phase ofthe propellant composition, combustibility and GWP after spraying 20mass % of the initial amount of the propellant composition charged,after spraying 40 mass %, after spraying 60 mass % and after spraying 80mass %, were obtained. Further, the compositions of the liquid phase andthe gaseous phase of the propellant composition in the pressurecontainer, combustibility and GWP after the propellant composition wassprayed until the pressure in the pressure container became equal toatmospheric pressure (at the time of completion of use) were obtained.The composition of the propellant composition was measured by gaschromatography, and the combustion test was conducted by the abovemethod. The results are shown in Table 2.

TABLE 2 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234ze(E) 1224yd(Z)1234ze(E) Liquid phase Gaseous phase GWP Initial 241.4 42.0 58.0 20.080.0 Incombustible Incombustible 1 20 231.9 47.3 52.7 23.0 77.0Incombustible Incombustible 1 40 217.6 54.8 45.2 27.6 72.4 IncombustibleIncombustible 1 60 192.4 66.6 33.4 36.3 63.7 Incombustible Incombustible1 80 136.7 87.1 12.9 61.4 38.6 Incombustible Incombustible 1 At the timeof 101.3 96.7 0.3 85.9 14.1 Incombustible Incombustible 1 completion(88.4)

As evident from Table 2, in the sprayer in Example 1, the propellantcomposition to be sprayed satisfied the requirements (1) and (2)throughout the entire period over which the sprayer was used.

Example 2

In the same manner as in Example 1 except that the composition of thepropellant composition filled in the pressure container was changed sothat the content of 1224yd(Z) was 45 mass % and the content of 1234ze(E)was 55 mass %, a sprayer was prepared, and the same spray test wascarried out. The results are shown in Table 3.

TABLE 3 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234ze(E) 1224yd(Z)1234ze(E) Liquid phase Gaseous phase GWP Initial 236.0 45.0 55.0 21.778.3 Incombustible Incombustible 1 20 225.7 50.6 49.4 24.9 75.1Incombustible Incombustible 1 40 210.1 58.4 41.6 30.0 70.0 IncombustibleIncombustible 1 60 182.9 70.6 29.4 39.9 60.1 Incombustible Incombustible1 80 126.0 90.2 9.8 67.7 32.3 Incombustible Incombustible 1 At the timeof 101.3 96.6 3.4 85.9 14.1 Incombustible Incombustible 1 completion(86.7)

As evident from Table 3, in the sprayer in Example 2, the propellantcomposition to be sprayed satisfied the requirements (1) and (2)throughout the entire period over which the sprayer was used.

Comparative Example 1

In the same manner as in Example 1 except that the composition of thepropellant composition filled in the pressure container was changed sothat the content of 1224yd(Z) was 40 mass % and the content of 1234ze(E)was 60 mass %, a sprayer was prepared, and the same spray test wascarried out. The results are shown in Table 4.

TABLE 4 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234ze(E) 1224yd(Z)1234ze(E) Liquid phase Gaseous phase GWP Initial 245.0 40.0 60.0 18.981.1 Incombustible Combustible 1 20 236.0 45.1 55.0 21.7 78.3Incombustible Incombustible 1 40 222.4 52.3 57.7 26.0 74.0 IncombustibleIncombustible 1 60 198.6 63.8 36.2 34.0 66.0 Incombustible Incombustible1 80 144.4 84.7 15.3 57.2 42.8 Incombustible Incombustible 1 At the timeof 101.3 96.6 3.4 85.9 14.1 Incombustible Incombustible 1 completion(89.4)

As evident from Table 4, in the sprayer in Comparative Example 1, thepropellant composition to be sprayed did not satisfy the requirement (1)at the initial stage of use.

Example 3

In the same manner as in Example 1 except that the propellantcomposition filled in the pressure container was changed to a propellantcomposition comprising 1224yd(Z) and 1234yf and having a content of1224yd(Z) of 67 mass % and a content of 1234yf of 33 mass %, a sprayerwas prepared, and the same spray test was carried out. The results areshown in Table 5. In Example 3, the pressure in the pressure containerbecame equal to atmospheric pressure before 80 mass % was sprayed, andthus evaluation after spraying 80 mass % was not conducted.

TABLE 5 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234yf 1224yd(Z) 1234yfLiquid phase Gaseous phase GWP Initial 239.8 67.0 33.0 30.2 69.8Incombustible Incombustible 1 20 208.0 75.5 24.5 38.0 62.0 IncombustibleIncombustible 1 40 163.0 85.9 14.1 52.5 47.5 Incombustible Incombustible1 60 110.1 96.1 3.9 80.2 19.8 Incombustible Incombustible 1 At the timeof 101.3 97.6 2.4 86.8 13.2 Incombustible Incombustible 1 completion(64.4)

As evident from Table 5, in the sprayer in Example 3, the propellantcomposition to be sprayed satisfied the requirements (1) and (2)throughout the entire period over which the sprayer was used.

Example 4

In the same manner as in Example 3 except that the composition of thepropellant composition filled in the pressure container was changed sothat the content of 1224yd(Z) was 70 mass % and the content of 1234yfwas 30 mass %, a sprayer was prepared, and the same spray test wascarried out. The results are shown in Table 6.

TABLE 6 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234yf 1224yd(Z) 1234yfLiquid phase Gaseous phase GWP Initial 228.8 70.0 30.0 32.7 67.3Incombustible Incombustible 1 20 195.7 78.5 21.5 41.4 58.6 IncombustibleIncombustible 1 40 150.6 88.5 11.5 57.6 42.4 Incombustible Incombustible1 60 103.6 97.2 2.8 85.0 15.0 Incombustible Incombustible 1 At the timeof 101.3 97.6 2.4 86.8 13.2 Incombustible Incombustible 1 completion(61.3)

As evident from Table 6, in the sprayer in Example 4, the propellantcomposition to be sprayed satisfied the requirements (1) and (2)throughout the entire period over which the sprayer was used.

Comparative Example 2

In the same manner as in Example 3 except that the composition of thepropellant composition filled in the pressure container was changed sothat the content of 1224yd(Z) was 65 mass % and the content of 1234yfwas 35 mass %, a sprayer was prepared, and the same spray test wascarried out. The results are shown in Table 7.

TABLE 7 Spray amount Pressure Composition of propellant composition(mass % to in [mass %] initial amount container Liquid phase Gaseousphase Combustibility charged) (kPa) 1224yd(Z) 1234yf 1224yd(Z) 1234yfLiquid phase Gaseous phase GWP Initial 246.9 65.0 35.0 28.7 71.3Incombustible Combustible 1 20 216.0 73.4 26.6 35.9 64.1 IncombustibleIncombustible 1 40 171.6 84.0 16.0 49.3 50.7 Incombustible Incombustible1 60 115.4 95.2 4.8 76.6 23.4 Incombustible Incombustible 1 At the timeof 101.3 97.6 2.4 86.8 13.2 Incombustible Incombustible 1 completion(66.3)

As evident from Table 7, in the sprayer in Comparative Example 2, thepropellant composition to be sprayed did not satisfy the requirement (1)at the initial stage of use.

REFERENCE SYMBOLS

10: sprayer (one component type), 20: sprayer (two component type), 1:container, 11: opening, 12: accommodating portion, 2: spray unit, 21:inlet, 22: spray nozzle, 23: nozzle, E: chemical agent, X_(I):propellant composition (initial), G_(I): gaseous phase portion(initial), L_(I): liquid phase portion (initial), X_(L): propellantcomposition (last), G_(L): gaseous phase portion (last), L_(L): liquidphase portion (last)

This application is a continuation of PCT Application No.PCT/JP2018/036101, filed on Sep. 27, 2018, which is based upon andclaims the benefit of priority from Japanese Patent Application No.2017-187614 filed on Sep. 28, 2017. The contents of those applicationsare incorporated herein by reference in their entireties.

1-6. (canceled)
 7. A sprayer, comprising: a container; a propellant composition containing 1-chloro-2,3,3,3-tetrafluoropropene contained under pressure as a liquid and a gas in the interior of the container; and a spray unit to spray the propellant composition out of the container, wherein the propellant composition satisfies the following requirements (1) and (2) throughout an entire period over a first state of the sprayer and a second state of the sprayer: (1) a no combustibility combustion test result in a combustion test on a mixture of the propellant composition and air in a container controlled at 60° C.±3° C. under 101.3 kPa±0.7 kPa as specified in ASTM E-681-09, such that no combustibility corresponds with the combustion test result when the mixture has no combustibility in the entire range of a proportion of the propellant composition to the total volume of the mixture being higher than 0 vol % and up to 100 vol % and when, in a gaseous phase in the vicinity of the center of the container, a fire is made by discharge ignition under 15 kV at 30 mA for 0.4 second, spread of flame is visually confirmed, and when the angle of spread of the flame upward is less than 90 degrees, and (2) the global warming potential (100 years) in accordance with Intergovernmental Panel on Climate Change (IPCC), Fifth Assessment Report, is less than 10, wherein the propellant composition further contains a hydrofluoroolefin, and the propellant composition is a non-azeotropic composition, wherein the first state of the sprayer: a first liquid volume of the propellant composition in the container is at most 90 vol % of a volume of the container at a first pressure, and wherein the second state of the sprayer: a second liquid volume of the propellant composition in the container is less than the first liquid volume at a second pressure, wherein the second pressure is atmospheric pressure.
 8. The sprayer according to claim 7, wherein the 1-chloro-2,3,3,3-tetrafluoropropene consists essentially of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1-chloro-2,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene to the total amount of 1-chloro-2,3,3,3-tetrafluoropropene is at least 80 mass % and at most 100 mass %.
 9. The sprayer according to claim 7, wherein the hydrofluoroolefin contains at least one member selected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene.
 10. The sprayer according to claim 7, wherein the propellant composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene is at least 20 mass % and less than 100 mass % to the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene in a gaseous phase portion in the container filled with the propellant composition so that the liquid phase portion is 90 vol %.
 11. The sprayer according to claim 7, wherein the propellant composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene is at least 30 mass % and less than 100 mass % to the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene in a gaseous phase portion in the container filled with the propellant composition so that the liquid phase portion is 90 vol %.
 12. The sprayer according to claim 7, wherein the propellant composition is a non-azeotropic mixture comprising one or more of (E)-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene.
 13. The sprayer according to claim 7, wherein the propellant composition consists essentially of (E)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, wherein the (E)-1-chloro-2,3,3,3-tetrafluoropropene is present in amount of 20-40 mass % and the (E)-1,3,3,3-tetrafluoropropene is present in an amount of 60-80 ass %, where mass % is based on the total mass of the propellant composition.
 14. The sprayer according to claim 7, wherein the propellant composition consists essentially of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, wherein the (Z)-1-chloro-2,3,3,3-tetrafluoropropene is present in an amount of 30-50 mass % and the (E)-1,3,3,3-tetrafluoropropene is present in an amount of 50-70 mass % based on the total mass of the propellant composition at the first state of the sprayer.
 15. The sprayer according to claim 7, wherein the pressure at the first state is up to 241 kPa.
 16. The sprayer according to claim 7, wherein the propellant composition contains from 42.0 to 66.6 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 58.0 to 33.4 mass % of (E)-1,3,3,3-tetrafluoropropene in a liquid state, and from 20.0-36.3 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 63.7 to 80.0 mass % of (E)-1-chloro-2,3,3,3-tetrafluoropropene in a gaseous state inside the container.
 17. The sprayer according to claim 7, wherein the propellant composition contains from 45.0-58.4 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 41.6 to 55.0 mass % of (E)-1,3,3,3-tetrafluoropropene in a liquid state inside the container, and from 21.7 to 30.0 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 70.0 to 78.3 mass % of (E)-1,3,3,3-tetrafluoropropene in a gaseous state inside the container.
 18. The sprayer according to claim 7, wherein at the second state when the pressure is atmospheric pressure, the container contains 11.6-13.3 mass % of the propellant composition based on the total mass of the propellant composition present in the container in an amount of 90 volume % in the liquid phase based on the volume of the container.
 19. The sprayer according to claim 7, wherein the propellant composition comprises from 67.0 to 85.9% of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 33.0 to 14.1 mass % of 2,3,3,3-tetrafluoropropene in a liquid state in the container, and from 30.2 to 52.5 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 47.5 to 69.8 mass % of 2,3,3,3-tetrafluoropropene in a gaseous state in the container.
 20. The sprayer according to claim 7, which is a one-component sprayer containing the propellant composition as the only liquid phase in the sprayer.
 21. The sprayer according to claim 7, which is a two-component sprayer containing mainly the propellant composition as the liquid phase in the sprayer. 